Hydrazine sulphonates of the diarylamine series



Patented Oct. 24, 1933 use HYDRAZENE SULEFHQNATES OF THE 7 DIARYLAMENE SERIES Arthur Zitscher, Vllilhelm Seidenfadcn, and Karl Eel 'nelr, @fienbach-on-the-Main,

Germany,

assignors to General Aniline tdlorlrs, Inn, New York, N. '52., a corporation of Delaware 4 Claims. (Cl. 26l)l28) Our present invention relates to hydrazine sulphonates of the diarylainine series, more particularly to those corresponding to the probable general formula.

They are of a great value for the production of azo-dyestuffs For this p pose they advantageously first mixed with combining components containing a hydroXy or an O-alkalimetal group whereof the adjacent position is capable of attaching an' aryl-azo-group. The compositions of matter thus produced are then brought onto the fibers in the presence of an alkali and the goods thus treated are thereafter subjected to a steaming operation.

As combining components of the aforesaid kind may be namedr 2-hydroxynaphthalena its nuclear substitution products as, for instance, aroylamino-hydroxynaphthalenes, (2-hydroXy-naphthalene-3-carbonyl)-arnino-aryls (as described in U. S. Patents No. 1,101,111 and No. 1,140,747), (fl-halogen or 6-arylainino-2-hydroxy-naphtha lene-S-carbonyl) amino-aryls (see German Patout No. 396,519 and British Patent No. 330,349), derivatives of 1hydroxy-naphthalene-d-carboxylic acid (see U. 5. Patent No. 1,453,660),

as, for instance, l-hydroxy-naphthalene4phenyl-ketone, compounds containing an acidic methylene group capable of being combined with 'diazocompounds, as, for instance, pyrazolones and derivatives of ,B-ketonaldehyde, for instance, aceto-acetyl-amino-aryls and di(aceto-acetyld0 amino)-ary1s (see U. S. Patents No. 1,594,864, No. 1,594,866, No. 1,59%,867, No. 1,580,709, No. 1,634,090), dihydroxy-quinolines (see U. S. Patents No. 1,820,039, No. 1,8e6,073 and No. 1546,07 1, -British Patent No. 332,940), (Z-hydroxy-carbazole-3-carbonyl)-amino-aryls, (2-hydroXy-benof the Society of Dyers andColorists, 1921, page 7.

zo-carbaZole-3-carbonyl)-amino-aryls, (2-hy' droxy-anthracene-3-oarbonyl) '-ainino-aryls.'

These dyeing preparations yield, when applied in an alkaline medium to fibers, by steaming only, insoluble aso-dyestufis on the fibers.

Such applying to the fibers consists in dyeing according to the one-bath-method or in printing. The dyebath or the printing paste or also the powderous dye preparations themselves are advantageously Xed with dyeing assistants having wetting, emulsifying or solvent properties, also with the additional agents customary in using nitrosamine-printing colors, as, for .instance, chromate. Furthermore, sulphur is advantageously added to the printing paste. Thereby, in some cases, the quickness and the evenness of the dyestuff formation is favorably influenced.

In order to further illustrate our invention the following examples are given, the parts being by weight and al temperatures in centigrade degrees; but we Wish it, however, to be understood that We are not limited to the particular conditions or specific products mentioned therein.

Example 1 32.9 parts of the sodium salt of 4'-lnthOXy diphenylarniiie-4l-diazosu1phonic acid (obtained according to U. S. Patent No. 1,897,ll0) are suspended in a solution of i l parts of calcined sodium carbonate in 500 parts of water and reduced ,by introducing slowly at (SO- 20 parts of sodiurnhydro'sulphite. The

reduction is finished when the reaction mass is dissolved and decolorized. sodium salt of the 4-methoxy-diphenylamine- 4-hydrazine-sulphonic acid precipitated from the filtrate by salting in form of colorless needles. It is worked up as usual. It corresponds to the probable formula:

43A parts of a nearly colorless filtering cake of a content of pure substance of 59.9% are thus obtained.

' Example 2 Then the niass is filtered warm and the nylamine-elAdihydrazinesulphonic acid is precipitated from the filtrate by salting in form of fine feebly colored needles. It corresponds probably to the formula:

After working up as usual 104 parts of a feebly colored paste containing 21.5% of pure substance are obtained.

' Example 3 To a diazosolution, prepared as usual from 16.7 parts of l-amino-2.5-dimetl'ioxy--2'.e'dinitrodi-- phenylamine, 25 parts of hydrochloric acid of 20 I jB., 300 parts of water and 4 parts of sodium ni- OCEa The precipitation is completed by salting and the sodium salt of the hydrazine sulphonic acid is worked up as usual. parts of a light redbroWn paste containing 50.2% of pure substance are thus obtained.

In an analogous manner the corresponding liydrazine-sulphonates are obtained by starting from other i-amino-diarylamines of the above mentioned kind, as for instance:

4-amino-3-chloro diphenylamine, l-amino-W- methyhdiphenylamine, 4-amino-4-n1ethylmerkapto-diphenylamine, l-aminoi-benzoylaminodiphenylamine, l-amino-B- (4' -"nethy1-.benzenesulphonyl) -diphenylamine, l-amino-3 (phenyl amino-carbonyl) -diphenylamine, l-arnino-e nitro-diphenylamine, 4amino-2.5-,dimethoxy-2- nitro l chloro diphenylamine, 2-( l-'aminophenyl-amino) -naphthalene.

All the dyestufis described in the table of U. S. Patent No. 1,920,542, may also be prepared according to our present invention if the dl'qtZO-S'lll-r prepare intermediates for the production of dyestuffs of good fastness properties which dyestuffs are insoluble in water and alkalies, it is to be understood that the aromatic nuclei of the general formulae appearing in the appended claims contain no substituents as are known to render organic compounds soluble in water or alkalies and to tend to depreciate the fastness of the dyestuff to alkalies. Substituents of this kind are the sulphonic acid, the carboxylic acid and the hydroxy group.

We claim: 7

1. The hydrazine-sulphonates of the diarylamine series corresponding to the probable general formula:

X-NI-I-R-l TH-NI-IS0salkali-metai wherein X means a naphthalene nucleus or a radical of the benzene series which may contain in the para-position to the NH-group a further l THl lI-ISO3-alkali-metal group and R means a radical of the benzene series, which compounds represent when dry yellowish to brownish powders and are valuable intermediates for the production of azodyestuffs.

2. The hydrazine-sulphonates of the diarylamine series corresponding to the probable general formula:

wherein the benzene nuclei may contain alkyl, alkcxy, aryloxy, halogen or nitro substituents and Y means hydrogen .or one of the aforesaid substituents or a second f 11c NN--SO3 alkali metal group, which compounds represent when dry yellowish to brownish powders and are valuable intermediates for the production of azo-dyestuffs.

3. The 4'-methoxy-dipheny1amine 4 hydrazine-sulphonate of the probable formula which compound represents nearly colorless crystals and is a valuable intermediate for the production of azo-dyestuffs.

a 4. The dipheny1amine-4.4- dihydrazine sulphonate of the probable formula ARTHUR ZITSCHER. W'ILHELM SEIDENFADEN. KARL JELLINEK. 

